High-transmittance anti-pollution fully-polished glaze and glazed brick using high-transmittance anti-pollution fully-polished glaze

Abstract

The invention relates to the technical field of ceramic glazes, and discloses a high-transmittance anti-pollution fully polished glaze and a glazed brick using the same. The high-transmittance anti-fouling full-polished glaze is prepared from the following raw materials in parts by mass: 25 to 30 parts of tea crystal feldspar, 5 to 10 parts of zinc oxide, 10 to 15 parts of barium carbonate, 2 to 5 parts of composite silicon carbide nanowire, 8 to 12 parts of calcined talc, 8 to 10 parts of kaolin, 8 to 10 parts of corundum, 23 to 27 parts of glass frit and 1 to 3 parts of zirconium silicate. The composite silicon carbide nanowires contain the modified silicon carbide nanowires and the magnesium aluminate spinel powder, and in the firing process of the fully polished glaze, the modified silicon carbide nanowires can be uniformly filled into a fully polished glaze layer through the magnesium aluminate spinel powder, so that the compactness, the mechanical property and the glossiness of the glaze layer are improved; the modified silicon carbide nanowires can be filled into pore defects introduced into a glaze layer by magnesium aluminate spinel powder, so that the glossiness, the antifouling property and the mechanical property of the fully polished glaze layer are improved.

Description

Technical Field

[0001] The invention relates to the technical field of ceramic glazes, in particular to a high-transparency and anti-fouling fully polished glaze and a glazed tile using the same. Background Art

[0002] Full-polished glaze is a special formula glaze that can be polished on the glaze surface. It is the last glaze applied to the brick. It is generally a transparent top glaze or a transparent convex flower glaze. The glaze surface is as smooth and bright as polished tiles. At the same time, its glaze pattern is rich like antique tiles, with thick or gorgeous colors. Transparent full-polished glaze can improve the surface properties of ceramic products without covering the top glaze and various flower glazes underneath, giving the brick products the characteristics of smoothness, brightness, and non-water absorption. It can also increase the strength of the brick products and improve the thermal stability and chemical stability of the brick products.

[0003] After the full-polished glaze components are mixed, they are ball-milled in water to form a full-polished glaze slurry. The full-polished glaze slurry is applied to the brick body and dried, fired, and polished. The resulting glazed tiles have excellent anti-fouling properties and glossiness. However, the full-polished glaze is prone to produce a large number of bubbles during firing, resulting in poor anti-fouling ability and loss of gloss in the glaze layer. In addition, the expansion coefficient of the glaze layer of the full-polished glazed tile is smaller than that of the tile body. The glaze layer is subjected to greater internal stress, causing it to deform during firing, which can easily lead to missed polishing or partial exposure of the bottom during polishing. Summary of the Invention

[0004] The present invention provides a highly transparent and anti-fouling fully polished glaze and a glazed tile using the same, which solves the problem that the fully polished glaze is deformed during firing, resulting in easy omissions or partial bottom exposure during polishing.

[0005] The technical solution of the present invention:

[0006] A high-transparency and anti-fouling full-polished glaze, comprising the following raw materials in parts by weight: 25-30 parts of smoky quartz feldspar, 5-10 parts of zinc oxide, 10-15 parts of barium carbonate, 2-5 parts of composite silicon carbide nanowires, 8-12 parts of calcined talc, 8-10 parts of kaolin, 8-10 parts of corundum, 23-27 parts of glass frit, and 1-3 parts of zirconium silicate;

[0007] A method for preparing a high-transparency, anti-fouling, fully polished glaze comprises the following steps:

[0008] Smoky quartz feldspar, zinc oxide, barium carbonate, composite silicon carbide nanowires, calcined talc, kaolin, corundum, glass frit and zirconium silicate are mixed evenly, crushed and passed through a 350-400 mesh sieve to obtain a high-transparency and anti-fouling full-polished glaze.

[0009] Furthermore, the composite silicon carbide nanowires are specifically prepared by the following steps:

[0010] A1. The silicon carbide nanowires were added to a nitric acid solution and a sulfuric acid solution, etched, removed, washed, and dried to obtain acid-etched silicon carbide nanowires;

[0011] A2. Add zirconium oxychloride octahydrate and acid-etched silicon carbide nanowires to deionized water and stir evenly. Then add ammonia, glycine, and potassium chloride. After stirring, the reaction is hydrothermally reacted at 170-190°C for 20-22 hours, cooled to room temperature, filtered, washed, and dried to obtain modified silicon carbide nanowires.

[0012] A3. Add modified silicon carbide nanowires, magnesium aluminum spinel powder, and hydroxypropyl methylcellulose to ethanol, stir evenly, heat to 80-90°C, continue stirring until the solvent evaporates, and cool to room temperature to obtain composite silicon carbide nanowires.

[0013] Furthermore, during the above-mentioned reaction A1, the silicon carbide nanowires can be etched with nitric acid and sulfuric acid to remove surface impurities and oxide layers. Nitric acid and sulfuric acid, as oxidants, can oxidize the Si-C covalent bonds on the surface of the silicon carbide nanowires, thereby forming a large number of Si-O bonds on the surface of the silicon carbide nanowires, thereby increasing their surface activity and facilitating the synthesis of nano-zirconium oxide on the surface of the silicon carbide nanowires.

[0014] Furthermore, during the above-mentioned reaction A2, the surface of the acid-etched silicon carbide nanowires contains a large number of hydrophilic hydroxyl groups, which can combine with the zirconium ions in the zirconium oxychloride octahydrate, so that the zirconium oxychloride octahydrate is adsorbed on the surface of the acid-etched silicon carbide nanowires. Ammonia water serves as a precipitant, and glycine and potassium chloride serve as auxiliary agents, which can react with the zirconium oxychloride octahydrate to generate zirconium hydroxide that is deposited on the surface of the acid-etched silicon carbide nanowires. The reaction continues, and the zirconium hydroxide decomposes under heat, thereby synthesizing nano-zirconium oxide with a particle size of 30-40 nm on the surface of the acid-etched silicon carbide nanowires to obtain modified silicon carbide nanowires.

[0015] Furthermore, during the above reaction A3, the magnesium aluminum spinel powder is loaded onto the surface of the modified silicon carbide nanowires through a binder, so that the magnesium aluminum spinel powder is evenly coated on the surface of the modified silicon carbide nanowires to obtain composite silicon carbide nanowires.

[0016] Furthermore, in step A1, the mass ratio of silicon carbide nanowires, nitric acid solution and sulfuric acid solution is (5-6):(25-35):(25-35).

[0017] Furthermore, in step A2, the mass ratio of zirconium oxychloride octahydrate, acid-etched silicon carbide nanowires, deionized water, ammonia water, glycine and potassium chloride is (0.4-0.6):(1.4-1.6):(90-110):(1.5-2.5):(0.3-0.5):(0.7-0.9).

[0018] Furthermore, in step A3, the mass ratio of modified silicon carbide nanowires, magnesium aluminum spinel powder, hydroxypropyl methylcellulose and ethanol is (2.4-2.6):(1-1.2):(0.2-0.4):(38-42).

[0019] Furthermore, silicon carbide nanowires with a diameter of 0.1-0.6 μm and a length of 50-100 μm were purchased from Changsha Saitai New Materials Co., Ltd.

[0020] Furthermore, the magnesium aluminum spinel powder has a particle size of 1-5 μm, a product grade of superior quality, and is purchased from Hubei Langbowan Biotechnology Co., Ltd.

[0021] A method for preparing a glazed tile, which is prepared using the above-mentioned high-transparency and anti-fouling full-glaze, comprises the following preparation steps:

[0022] S1. The high-transparency anti-fouling full-polished glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate and water were mixed and ball-milled to obtain a full-polished glaze slurry;

[0023] S2. Apply base glaze, printed glaze and top glaze on the brick in sequence to form a glazed tile base. Apply full-glazed slurry on the glazed tile base by pouring glaze. After drying, firing and polishing, the glazed tile is obtained.

[0024] Furthermore, in step S1, the mass ratio of high-transparency and anti-fouling full-polished glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate and water is (70-75):(0.1-0.2):(0.2-0.3):(30-35).

[0025] Furthermore, in step S1, ball milling is performed in a ball mill, the grinding balls are zirconium balls with a diameter of 8-10 mm, the ball-to-material ratio is (2-3):1, and the ball milling time is 18-22 h.

[0026] Furthermore, in step S2, the glaze specific gravity is 1.5-1.6, and the glaze amount can be 500-550g / m 2 .

[0027] Furthermore, in step S2, the drying temperature is 80-110°C, and the drying time is 20-30 minutes.

[0028] Furthermore, in step S2, the firing temperature is 1200-1220°C, and the firing time is 60-80 minutes.

[0029] Furthermore, in step S2, polishing is performed using diamond particles with a particle size of 800-1000 mesh, a polishing time of 4-6 minutes, and a polishing pressure of 0.03-0.1 MPa.

[0030] The present invention has the following beneficial effects:

[0031] (1) In the technical solution of the present invention, silicon carbide nanowires are etched with nitric acid and sulfuric acid, so that a large number of hydrophilic groups, silanol groups, are formed on the surface of the silicon carbide nanowires, thereby improving the dispersibility of the silicon carbide nanowires and facilitating the synthesis of a large number of nano-zirconium oxide on the surface of the silicon carbide nanowires; nano-zirconium oxide is synthesized on the surface of the acid-etched silicon carbide nanowires to obtain modified silicon carbide nanowires. On the one hand, the acid-etched silicon carbide nanowires serve as carriers of nano-zirconium oxide, thereby improving the dispersibility of nano-zirconium oxide in the full-polished glaze slurry. Moreover, when the full-polished glaze slurry is applied during the firing process, nano-zirconium oxide pins the grain boundaries, inhibits grain growth, and improves the density of the full-polished glaze layer. The dense glaze layer The structure can reduce the attachment of stains and bacteria, thereby improving the anti-fouling ability and glossiness of the glazed tiles. On the other hand, silicon carbide nanowires have an excellent aspect ratio and form a network skeleton in the full-polished glaze layer. Silicon carbide nanowires and nano-zirconia can fill the gaps in the full-polished glaze layer, significantly improving the scratch resistance of the glaze layer and reducing wear during daily use. In addition, silicon carbide nanowires and nano-zirconia have excellent thermal stability, which can alleviate the thermal stress of the glaze layer during temperature changes, avoid the glaze layer expansion coefficient being smaller than the tile body, and the glaze layer being subjected to greater internal stress, causing it to deform during firing, thereby improving the glaze layer's anti-fouling performance, glossiness and mechanical properties.

[0032] (2) In the technical solution of the present invention, magnesium aluminum spinel powder is uniformly coated on the surface of the modified silicon carbide nanowires to obtain composite silicon carbide nanowires; on the one hand, magnesium aluminum spinel powder has high hardness, high melting point and excellent chemical stability and thermal stability, and its thermal expansion coefficient matches that of the ceramic tile body, avoiding a large difference in the expansion coefficient of the glaze layer and the ceramic tile body, which causes the glaze layer to be subjected to large internal stress and deforms during firing; on the other hand, during the firing process of the full-polished glaze, magnesium aluminum spinel powder can provide more alumina components, which can capture the free oxygen in the full-polished glaze to form a four-coordinated structure and enter the silicon-oxygen network structure of the full-polished glaze, thereby contributing to the formation of the glaze network structure and improving the chemical stability, hardness and elasticity;

[0033] Coating magnesium aluminum spinel powder on the surface of modified silicon carbide nanowires can improve the dispersion of fine-particle magnesium aluminum spinel powder in the full-polished glaze. During the firing process, the modified silicon carbide nanowires can be evenly filled into the full-polished glaze layer through the magnesium aluminum spinel powder, thereby improving the density, mechanical properties and glossiness of the glaze layer. In addition, the nano-zirconium oxide on the surface of the modified silicon carbide nanowires can be filled into the pore defects introduced by the magnesium aluminum spinel powder in the glaze layer, thereby avoiding the magnesium aluminum spinel powder introducing pores in the full-polished glaze layer, resulting in a decrease in the gloss, anti-fouling and mechanical properties of the full-polished glaze layer. DETAILED DESCRIPTION

[0034] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0035] The raw materials used in the examples of the present invention are as follows, and all reagents used are of analytical grade.

[0036] Among them, smoky quartz feldspar and glass frit were purchased from Foshan Sanjingshi Ceramic Glaze Co., Ltd. The glass frit is a barium-free frit with the chemical composition of SiO2: 67%, Al2O3: 5.0%, CaO: 20.5%, MgO: 2.3%, K2O: 2.8%, ZnO: 2.3%, and Na2O: 0.8%.

[0037] The glazed brick base has a thickness of 12 mm and was purchased from Zibo Shuncheng Architectural Ceramics Co., Ltd.

[0038] Silicon carbide nanowires with a diameter of 0.5 μm and a length of 70 μm were purchased from Changsha Saitai New Materials Co., Ltd.

[0039] The particle size of magnesium aluminum spinel powder is 2 μm, the product grade is superior, and it was purchased from Hubei Langbowan Biopharmaceutical Co., Ltd.

[0040] Example 1

[0041] A high-transparency and stain-resistant full-polished glaze, comprising the following raw materials in parts by weight: 25 parts of smoky quartz feldspar, 5 parts of zinc oxide, 10 parts of barium carbonate, 2 parts of composite silicon carbide nanowires, 8 parts of calcined talc, 8 parts of kaolin, 8 parts of corundum, 23 parts of glass frit, and 1 part of zirconium silicate;

[0042] A method for preparing a high-transparency, anti-fouling, fully polished glaze comprises the following steps:

[0043] Smoky quartz feldspar, zinc oxide, barium carbonate, composite silicon carbide nanowires, calcined talc, kaolin, corundum, glass frit and zirconium silicate are mixed evenly, crushed and passed through a 350-mesh sieve to obtain a high-transparency and anti-fouling full-polished glaze.

[0044] A method for preparing glazed tiles comprises the following steps:

[0045] S1. The high-transparency and anti-fouling full-polished glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate and water were mixed and ball-milled in a ball mill. The grinding balls were 8 mm in diameter zirconium balls, the ball-to-material ratio was 2:1, and the ball-milling time was 18 h to obtain a full-polished glaze slurry; the mass ratio of high-transparency and anti-fouling full-polished glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate and water was 70:0.1:0.2:30;

[0046] S2. Control the glaze density of the full-polished glaze slurry to 1.5, and the glaze amount can be 500g / m 2 The full-glaze slurry is applied to the glazed tile substrate by pouring glaze, dried at 80℃ for 20min, fired at 1200℃ for 60min, and polished with 1000-mesh diamond particles for 5min at a polishing pressure of 0.05MPa to obtain the glazed tile.

[0047] The composite silicon carbide nanowires are specifically prepared by the following steps:

[0048] A1. SiC nanowires were added to a 0.5 M nitric acid solution and a 0.5 M sulfuric acid solution and etched for 1 minute. The resulting solution was then removed and washed with deionized water until the pH of the solution was neutral. The solution was then dried in a 70°C oven for 10 minutes to obtain acid-etched SiC nanowires. The mass ratio of SiC nanowires, nitric acid solution, and sulfuric acid solution was 5:25:25.

[0049] A2. Zirconium oxychloride octahydrate and acid-etched silicon carbide nanowires were added to deionized water and stirred evenly. Ammonia, glycine, and potassium chloride were then added. The mixture was stirred at 85°C for 10 minutes. The mixture was placed in a reactor and hydrothermally reacted at 170°C for 20 hours. The mixture was cooled to room temperature, filtered, washed three times with deionized water, and dried in an oven at 80°C for 3 hours to obtain modified silicon carbide nanowires. The mass ratio of zirconium oxychloride octahydrate, acid-etched silicon carbide nanowires, deionized water, ammonia, glycine, and potassium chloride was 0.4:1.4:90:1.5:0.3:0.7.

[0050] A3. Modified silicon carbide nanowires, magnesium aluminum spinel powder, and hydroxypropyl methylcellulose were added to ethanol and stirred evenly. The mixture was heated to 85°C and continued to stir until the solvent evaporated. The mixture was then cooled to room temperature to obtain composite silicon carbide nanowires. The mass ratio of modified silicon carbide nanowires, magnesium aluminum spinel powder, hydroxypropyl methylcellulose, and ethanol was 2.4:1:0.2:38.

[0051] Example 2

[0052] A high-transparency and stain-resistant full-polished glaze, comprising the following raw materials in parts by weight: 28 parts of smoky quartz feldspar, 8 parts of zinc oxide, 13 parts of barium carbonate, 3 parts of composite silicon carbide nanowires, 10 parts of calcined talc, 9 parts of kaolin, 9 parts of corundum, 25 parts of glass frit, and 2 parts of zirconium silicate;

[0053] A method for preparing a high-transparency, anti-fouling, fully polished glaze comprises the following steps:

[0054] Smoky quartz feldspar, zinc oxide, barium carbonate, composite silicon carbide nanowires, calcined talc, kaolin, corundum, glass frit and zirconium silicate are mixed evenly, crushed and passed through a 380-mesh sieve to obtain a high-transparency and anti-fouling full-polished glaze.

[0055] A method for preparing glazed tiles comprises the following steps:

[0056] S1. The high-transparency anti-fouling full-polished glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate and water were mixed and ball-milled in a ball mill. The grinding balls were zirconium balls with a diameter of 9 mm. The ball-to-material ratio was 2.5:1 and the ball-to-material ratio was 20 h to obtain a full-polished glaze slurry. The mass ratio of high-transparency anti-fouling full-polished glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate and water was 73:0.15:0.25:33.

[0057] S2. Control the glaze density of the full-polished glaze slurry to 1.55, and the glaze amount can be 530g / m 2 The full-glaze slurry is applied to the glazed tile substrate by pouring glaze, dried at 100℃ for 25min, fired at 1210℃ for 70min, and polished with 1000-mesh diamond particles for 5min at a polishing pressure of 0.05MPa to obtain the glazed tile.

[0058] The composite silicon carbide nanowires are specifically prepared by the following steps:

[0059] A1. SiC nanowires were added to a 0.5 M nitric acid solution and a 0.5 M sulfuric acid solution and etched for 1 minute. The resulting silicon carbide nanowires were then removed and washed with deionized water until the pH of the washing solution was neutral. The resulting solution was then dried in a 70°C oven for 10 minutes to obtain acid-etched SiC nanowires. The mass ratio of SiC nanowires, nitric acid solution, and sulfuric acid solution was 5.5:30:30.

[0060] A2. Zirconium oxychloride octahydrate and acid-etched silicon carbide nanowires were added to deionized water and stirred evenly. Ammonia, glycine, and potassium chloride were then added. The mixture was stirred at 85°C for 10 minutes. The mixture was placed in a reactor and hydrothermally reacted at 180°C for 21 hours. The mixture was cooled to room temperature, filtered, washed three times with deionized water, and dried in an oven at 80°C for 3 hours to obtain modified silicon carbide nanowires. The mass ratio of zirconium oxychloride octahydrate, acid-etched silicon carbide nanowires, deionized water, ammonia, glycine, and potassium chloride was 0.5:1.5:100:2:0.4:0.8.

[0061] A3. Add modified silicon carbide nanowires, magnesium aluminum spinel powder, and hydroxypropyl methylcellulose to ethanol, stir evenly, heat to 85°C, continue stirring until the solvent evaporates, and cool to room temperature to obtain composite silicon carbide nanowires. The mass ratio of modified silicon carbide nanowires, magnesium aluminum spinel powder, hydroxypropyl methylcellulose, and ethanol is 2.5:1.1:0.3:40.

[0062] Example 3

[0063] A high-transparency and stain-resistant full-polished glaze, comprising the following raw materials in parts by weight: 30 parts of smoky quartz feldspar, 10 parts of zinc oxide, 15 parts of barium carbonate, 5 parts of composite silicon carbide nanowires, 12 parts of calcined talc, 10 parts of kaolin, 10 parts of corundum, 27 parts of glass frit, and 3 parts of zirconium silicate;

[0064] A method for preparing a high-transparency, anti-fouling, fully polished glaze comprises the following steps:

[0065] Smoky quartz feldspar, zinc oxide, barium carbonate, composite silicon carbide nanowires, calcined talc, kaolin, corundum, glass frit and zirconium silicate are mixed evenly, crushed and passed through a 400-mesh sieve to obtain a high-transparency and anti-fouling full-polished glaze.

[0066] A method for preparing glazed tiles comprises the following steps:

[0067] S1. The high-transparency and anti-fouling full-polished glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate, and water were mixed and ball-milled in a ball mill with 10 mm diameter zirconium balls at a ball-to-material ratio of 3:1 for 22 h to obtain a full-polished glaze slurry; the mass ratio of high-transparency and anti-fouling full-polished glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate, and water was 75:0.2:0.3:35;

[0068] S2. Control the glaze density of the full-polished glaze slurry to 1.6, and the glaze amount can be 550g / m 2 The full-glaze slurry is applied to the glazed tile substrate by pouring glaze, dried at 110℃ for 30min, fired at 1220℃ for 80min, and polished with 1000-mesh diamond particles for 5min at a polishing pressure of 0.05MPa to obtain the glazed tile.

[0069] The composite silicon carbide nanowires are specifically prepared by the following steps:

[0070] A1. SiC nanowires were added to a 0.5 M nitric acid solution and a 0.5 M sulfuric acid solution and etched for 1 minute. The resulting silicon carbide nanowires were then removed and washed with deionized water until the pH of the solution was neutral. The resulting solution was then dried in a 70°C oven for 10 minutes to obtain acid-etched SiC nanowires. The mass ratio of SiC nanowires, nitric acid solution, and sulfuric acid solution was 6:35:35.

[0071] A2. Zirconium oxychloride octahydrate and acid-etched silicon carbide nanowires were added to deionized water and stirred evenly. Ammonia, glycine, and potassium chloride were then added. The mixture was stirred at 85°C for 10 minutes. The mixture was placed in a reactor and hydrothermally reacted at 190°C for 22 hours. The mixture was cooled to room temperature, filtered, washed three times with deionized water, and dried in an oven at 80°C for 3 hours to obtain modified silicon carbide nanowires. The mass ratio of zirconium oxychloride octahydrate, acid-etched silicon carbide nanowires, deionized water, ammonia, glycine, and potassium chloride was 0.6:1.6:110:2.5:0.5:0.9.

[0072] A3. Modified silicon carbide nanowires, magnesium aluminum spinel powder, and hydroxypropyl methylcellulose were added to ethanol and stirred evenly. The mixture was heated to 85°C and continued to stir until the solvent evaporated. The mixture was then cooled to room temperature to obtain composite silicon carbide nanowires. The mass ratio of modified silicon carbide nanowires, magnesium aluminum spinel powder, hydroxypropyl methylcellulose, and ethanol was 2.6:1.2:0.4:42.

[0073] Comparative Example 1

[0074] A high-transparency and stain-resistant full-polished glaze, comprising the following raw materials in parts by weight: 30 parts of smoky quartz feldspar, 10 parts of zinc oxide, 15 parts of barium carbonate, 5 parts of composite silicon carbide nanowires, 12 parts of calcined talc, 10 parts of kaolin, 10 parts of corundum, 27 parts of glass frit, and 3 parts of zirconium silicate;

[0075] A method for preparing a high-transparency, anti-fouling, fully polished glaze comprises the following steps:

[0076] Smoky quartz feldspar, zinc oxide, barium carbonate, composite silicon carbide nanowires, calcined talc, kaolin, corundum, glass frit and zirconium silicate are mixed evenly, crushed and passed through a 400-mesh sieve to obtain a high-transparency and anti-fouling full-polished glaze.

[0077] A method for preparing glazed tiles comprises the following steps:

[0078] S1. The high-transparency and anti-fouling full-polished glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate, and water were mixed and ball-milled in a ball mill with 10 mm diameter zirconium balls at a ball-to-material ratio of 3:1 for 22 h to obtain a full-polished glaze slurry; the mass ratio of high-transparency and anti-fouling full-polished glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate, and water was 75:0.2:0.3:35;

[0079] S2. Control the glaze density of the full-polished glaze slurry to 1.6, and the glaze amount can be 550g / m 2 The full-glaze slurry is applied to the glazed tile substrate by pouring glaze, dried at 110℃ for 30min, fired at 1220℃ for 80min, and polished with 1000-mesh diamond particles for 5min at a polishing pressure of 0.05MPa to obtain the glazed tile.

[0080] The composite silicon carbide nanowires are specifically prepared by the following steps:

[0081] A1. Zirconium oxychloride octahydrate and silicon carbide nanowires were added to deionized water and stirred uniformly. Ammonia, glycine, and potassium chloride were then added. The mixture was stirred at 85°C for 10 minutes. The mixture was placed in a reactor and hydrothermally reacted at 190°C for 22 hours. The mixture was cooled to room temperature, filtered, washed three times with deionized water, and dried in an oven at 80°C for 3 hours to obtain modified silicon carbide nanowires. The mass ratio of zirconium oxychloride octahydrate, silicon carbide nanowires, deionized water, ammonia, glycine, and potassium chloride was 0.6:1.6:110:2.5:0.5:0.9.

[0082] A2. Modified silicon carbide nanowires, magnesium aluminum spinel powder, and hydroxypropyl methylcellulose were added to ethanol and stirred evenly. The mixture was heated to 85°C and stirred until the solvent evaporated. The mixture was then cooled to room temperature to obtain composite silicon carbide nanowires. The mass ratio of modified silicon carbide nanowires, magnesium aluminum spinel powder, hydroxypropyl methylcellulose, and ethanol was 2.6:1.2:0.4:42.

[0083] Comparative Example 2

[0084] A high-transparency and stain-resistant full-polished glaze, comprising the following raw materials in parts by weight: 30 parts of smoky quartz feldspar, 10 parts of zinc oxide, 15 parts of barium carbonate, 5 parts of composite silicon carbide nanowires, 12 parts of calcined talc, 10 parts of kaolin, 10 parts of corundum, 27 parts of glass frit, and 3 parts of zirconium silicate;

[0085] A method for preparing a high-transparency, anti-fouling, fully polished glaze comprises the following steps:

[0086] Smoky quartz feldspar, zinc oxide, barium carbonate, composite silicon carbide nanowires, calcined talc, kaolin, corundum, glass frit and zirconium silicate are mixed evenly, crushed and passed through a 400-mesh sieve to obtain a high-transparency and anti-fouling full-polished glaze.

[0087] A method for preparing glazed tiles comprises the following steps:

[0088] S1. The high-transparency and anti-fouling full-polished glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate, and water were mixed and ball-milled in a ball mill with 10 mm diameter zirconium balls at a ball-to-material ratio of 3:1 for 22 h to obtain a full-polished glaze slurry; the mass ratio of high-transparency and anti-fouling full-polished glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate, and water was 75:0.2:0.3:35;

[0089] S2. Control the glaze density of the full-polished glaze slurry to 1.6, and the glaze amount can be 550g / m 2 The full-glaze slurry is applied to the glazed tile substrate by pouring glaze, dried at 110℃ for 30min, fired at 1220℃ for 80min, and polished with 1000-mesh diamond particles for 5min at a polishing pressure of 0.05MPa to obtain the glazed tile.

[0090] The composite silicon carbide nanowires are specifically prepared by the following steps:

[0091] A1. SiC nanowires were added to a 0.5 M nitric acid solution and a 0.5 M sulfuric acid solution and etched for 1 minute. The resulting silicon carbide nanowires were then removed and washed with deionized water until the pH of the solution was neutral. The resulting solution was then dried in a 70°C oven for 10 minutes to obtain acid-etched SiC nanowires. The mass ratio of SiC nanowires, nitric acid solution, and sulfuric acid solution was 6:35:35.

[0092] A2. Add acid-etched silicon carbide nanowires, magnesium aluminum spinel powder, and hydroxypropyl methylcellulose to ethanol, stir evenly, heat to 85°C, continue stirring until the solvent evaporates, and cool to room temperature to obtain composite silicon carbide nanowires. The mass ratio of acid-etched silicon carbide nanowires, magnesium aluminum spinel powder, hydroxypropyl methylcellulose, and ethanol is 2.6:1.2:0.4:42.

[0093] Comparative Example 3

[0094] A high-transparency and anti-fouling full-polished glaze, comprising the following raw materials in parts by weight: 30 parts of smoky quartz feldspar, 10 parts of zinc oxide, 15 parts of barium carbonate, 5 parts of composite nano-zirconium oxide, 12 parts of calcined talc, 10 parts of kaolin, 10 parts of corundum, 27 parts of glass frit, and 3 parts of zirconium silicate;

[0095] A method for preparing a high-transparency, anti-fouling, fully polished glaze comprises the following steps:

[0096] Smoky quartz feldspar, zinc oxide, barium carbonate, composite nano zirconium oxide, calcined talc, kaolin, corundum, glass frit and zirconium silicate are mixed evenly, crushed and passed through a 400-mesh sieve to obtain a highly transparent and stain-resistant full-polished glaze.

[0097] A method for preparing glazed tiles comprises the following steps:

[0098] S1. The high-transparency and anti-fouling full-polished glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate, and water were mixed and ball-milled in a ball mill with 10 mm diameter zirconium balls at a ball-to-material ratio of 3:1 for 22 h to obtain a full-polished glaze slurry; the mass ratio of high-transparency and anti-fouling full-polished glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate, and water was 75:0.2:0.3:35;

[0099] S2. Control the glaze density of the full-polished glaze slurry to 1.6, and the glaze amount can be 550g / m 2 The full-glaze slurry is applied to the glazed tile substrate by pouring glaze, dried at 110℃ for 30min, fired at 1220℃ for 80min, and polished with 1000-mesh diamond particles for 5min at a polishing pressure of 0.05MPa to obtain the glazed tile.

[0100] Composite nano-zirconia is specifically prepared by the following steps:

[0101] A1. Zirconium oxychloride octahydrate was added to deionized water and stirred thoroughly. Ammonia, glycine, and potassium chloride were then added. The mixture was stirred at 85°C for 10 minutes. The mixture was placed in a reactor and hydrothermally reacted at 190°C for 22 hours. The mixture was cooled to room temperature, filtered, washed three times with deionized water, and dried in an oven at 80°C for 3 hours to obtain nanozirconium oxide. The mass ratio of zirconium oxychloride octahydrate, acid-etched silicon carbide nanowires, deionized water, ammonia, glycine, and potassium chloride was 0.6:1.6:110:2.5:0.5:0.9.

[0102] A2. Add nano-zirconia, magnesium aluminum spinel powder, and hydroxypropyl methylcellulose to ethanol, stir evenly, heat to 85°C, continue stirring until the solvent evaporates, and cool to room temperature to obtain composite nano-zirconia; the mass ratio of nano-zirconia, magnesium aluminum spinel powder, hydroxypropyl methylcellulose, and ethanol is 2.6:1.2:0.4:42.

[0103] Comparative Example 4

[0104] A high-transparency and stain-resistant full-polished glaze, comprising the following raw materials in parts by weight: 30 parts of smoky quartz feldspar, 10 parts of zinc oxide, 15 parts of barium carbonate, 5 parts of composite silicon carbide nanowires, 12 parts of calcined talc, 10 parts of kaolin, 10 parts of corundum, 27 parts of glass frit, and 3 parts of zirconium silicate;

[0105] A method for preparing a high-transparency, anti-fouling, fully polished glaze comprises the following steps:

[0106] Smoky quartz feldspar, zinc oxide, barium carbonate, composite silicon carbide nanowires, calcined talc, kaolin, corundum, glass frit and zirconium silicate are mixed evenly, crushed and passed through a 400-mesh sieve to obtain a high-transparency and anti-fouling full-polished glaze.

[0107] A method for preparing glazed tiles comprises the following steps:

[0108] S1. The high-transparency and anti-fouling full-polished glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate, and water were mixed and ball-milled in a ball mill with 10 mm diameter zirconium balls at a ball-to-material ratio of 3:1 for 22 h to obtain a full-polished glaze slurry; the mass ratio of high-transparency and anti-fouling full-polished glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate, and water was 75:0.2:0.3:35;

[0109] S2. Control the glaze density of the full-polished glaze slurry to 1.6, and the glaze amount can be 550g / m 2The full-glaze slurry is applied to the glazed tile substrate by pouring glaze, dried at 110℃ for 30min, fired at 1220℃ for 80min, and polished with 1000-mesh diamond particles for 5min at a polishing pressure of 0.05MPa to obtain the glazed tile.

[0110] The composite silicon carbide nanowires are specifically prepared by the following steps:

[0111] A1. SiC nanowires were added to a 0.5 M nitric acid solution and a 0.5 M sulfuric acid solution and etched for 1 minute. The resulting silicon carbide nanowires were then removed and washed with deionized water until the pH of the solution was neutral. The resulting solution was then dried in a 70°C oven for 10 minutes to obtain acid-etched SiC nanowires. The mass ratio of SiC nanowires, nitric acid solution, and sulfuric acid solution was 6:35:35.

[0112] A2. Zirconium oxychloride octahydrate and acid-etched silicon carbide nanowires were added to deionized water and stirred evenly. Ammonia, glycine, and potassium chloride were then added. The mixture was stirred at 85°C for 10 minutes. The mixture was placed in a reactor and hydrothermally reacted at 190°C for 22 hours. The mixture was cooled to room temperature, filtered, washed three times with deionized water, and dried in an oven at 80°C for 3 hours to obtain modified silicon carbide nanowires. The mass ratio of zirconium oxychloride octahydrate, acid-etched silicon carbide nanowires, deionized water, ammonia, glycine, and potassium chloride was 0.6:1.6:110:2.5:0.5:0.9.

[0113] A3. Add modified silicon carbide nanowires and magnesium aluminum spinel powder to ethanol, stir evenly, heat to 85°C, continue stirring until the solvent evaporates, and cool to room temperature to obtain composite silicon carbide nanowires; the mass ratio of modified silicon carbide nanowires, magnesium aluminum spinel powder, and ethanol is 2.6:1.2:42.

[0114] Comparative Example 5

[0115] A high-transparency and stain-resistant full-polished glaze, comprising the following raw materials in parts by weight: 30 parts of smoky quartz feldspar, 10 parts of zinc oxide, 15 parts of barium carbonate, 5 parts of composite silicon carbide nanowires, 12 parts of calcined talc, 10 parts of kaolin, 10 parts of corundum, 27 parts of glass frit, and 3 parts of zirconium silicate;

[0116] A method for preparing a high-transparency, anti-fouling, fully polished glaze comprises the following steps:

[0117] Smoky quartz feldspar, zinc oxide, barium carbonate, composite silicon carbide nanowires, calcined talc, kaolin, corundum, glass frit and zirconium silicate are mixed evenly, crushed and passed through a 400-mesh sieve to obtain a high-transparency and anti-fouling full-polished glaze.

[0118] A method for preparing glazed tiles comprises the following steps:

[0119] S1. The high-transparency and anti-fouling full-polished glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate, and water were mixed and ball-milled in a ball mill with 10 mm diameter zirconium balls at a ball-to-material ratio of 3:1 for 22 h to obtain a full-polished glaze slurry; the mass ratio of high-transparency and anti-fouling full-polished glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate, and water was 75:0.2:0.3:35;

[0120] S2. Control the glaze density of the full-polished glaze slurry to 1.6, and the glaze amount can be 550g / m 2 The full-glaze slurry is applied to the glazed tile substrate by pouring glaze, dried at 110℃ for 30min, fired at 1220℃ for 80min, and polished with 1000-mesh diamond particles for 5min at a polishing pressure of 0.05MPa to obtain the glazed tile.

[0121] The composite silicon carbide nanowires are specifically prepared by the following steps:

[0122] A1. SiC nanowires were added to a 0.5 M nitric acid solution and a 0.5 M sulfuric acid solution and etched for 1 minute. The resulting silicon carbide nanowires were then removed and washed with deionized water until the pH of the solution was neutral. The resulting solution was then dried in a 70°C oven for 10 minutes to obtain acid-etched SiC nanowires. The mass ratio of SiC nanowires, nitric acid solution, and sulfuric acid solution was 6:35:35.

[0123] A2. Zirconium oxychloride octahydrate and acid-etched silicon carbide nanowires were added to deionized water and stirred evenly. Ammonia, glycine, and potassium chloride were then added. The mixture was stirred at 85°C for 10 minutes. The mixture was placed in a reactor and hydrothermally reacted at 190°C for 22 hours. The mixture was cooled to room temperature, filtered, washed three times with deionized water, and dried in an oven at 80°C for 3 hours to obtain modified silicon carbide nanowires. The mass ratio of zirconium oxychloride octahydrate, acid-etched silicon carbide nanowires, deionized water, ammonia, glycine, and potassium chloride was 0.6:1.6:110:2.5:0.5:0.9.

[0124] A3. Modified silicon carbide nanowires and hydroxypropyl methylcellulose were added to ethanol, stirred evenly, heated to 85°C, and stirred until the solvent evaporated. The mixture was then cooled to room temperature to obtain composite silicon carbide nanowires. The mass ratio of modified silicon carbide nanowires, hydroxypropyl methylcellulose, and ethanol was 2.6:0.4:42.

[0125] The performance of the glazed tiles prepared with high-transmittance and anti-fouling full-glaze provided in Examples 1-3 and Comparative Examples 1-5 is now tested.

[0126] Vickers hardness test: A diamond with a regular tetrahedral shape and an angle of 136 degrees was used as an indenter, with a load of 1000 g and a load time of 30 s to perform a Vickers hardness test on the glazed tiles prepared above.

[0127] Anti-fouling performance test: The anti-fouling performance test of the glazed tiles prepared above was carried out according to the GB / T3810.14-2016 standard.

[0128] Glossiness test: The glossiness of the glazed tiles prepared above was tested according to GB / T13891.14-2008 standard.

[0129] Wear resistance test: The wear loss of the glazed tiles prepared above was tested according to GB / T3810.7-2016 standard (g / 12000 revolutions);

[0130] As shown in Table 1 below.

[0131] Table 1 Performance test of glazed tiles prepared in Examples 1-3 and Comparative Examples 1-5

[0132] project Vickers hardness / HV Anti-fouling grade / level Glossiness / ° Wear loss (g / 12000 revolutions) Example 1 586.3 5 97.6 0.07 Example 2 587.8 5 97.9 0.06 Example 3 585.7 5 97.2 0.07 Comparative Example 1 523.6 4 92.5 0.11 Comparative Example 2 513.9 3 90.1 0.15 Comparative Example 3 511.4 3 89.6 0.18 Comparative Example 4 505.1 3 89.7 0.17 Comparative Example 5 486.5 3 85.1 0.14

[0133] It can be seen from the data in Table 1 that the glazed tiles prepared using the high-transparency and anti-fouling full-glaze provided in Examples 1-3 have good anti-fouling performance, glossiness and mechanical properties.

[0134] In Comparative Example 1, the acid-etched silicon carbide nanowires were replaced with composite silicon carbide nanowires prepared from silicon carbide nanowires and added to the full-polished glaze. The anti-fouling performance, mechanical properties and glossiness of the glazed tiles prepared decreased, proving that the etching of silicon carbide nanowires with nitric acid and sulfuric acid is conducive to the synthesis of a large amount of nano-zirconium oxide on the surface of the silicon carbide nanowires, thereby inhibiting grain growth and improving the density of the full-polished glaze layer. The dense glaze layer structure can reduce the attachment of stains and bacteria, thereby improving the anti-fouling ability and glossiness of the glazed tiles.

[0135] In Comparative Example 2, the modified silicon carbide nanowires are replaced with composite silicon carbide nanowires prepared by acid-etched silicon carbide nanowires and added to the full-polished glaze. The anti-fouling performance, mechanical properties and glossiness of the glazed tiles used for preparation are reduced, which proves that nano-zirconium oxide is synthesized on the surface of the acid-etched silicon carbide nanowires. Nano-zirconium oxide pins the grain boundaries, inhibits grain growth, improves the density of the full-polished glaze layer, and fills the gaps in the full-polished glaze layer, significantly improving the scratch resistance of the glaze layer and reducing wear in daily use. In addition, it has excellent thermal stability and can relieve the thermal stress of the glaze layer when the temperature changes.

[0136] In Comparative Example 3, the composite nano-zirconium oxide prepared by adding acid-etched silicon carbide nanowires was added to the full-polished glaze. The anti-fouling performance, mechanical properties and glossiness of the glazed tiles prepared decreased, proving that silicon carbide nanowires have an excellent aspect ratio and form a network skeleton in the full-polished glaze layer. In addition, silicon carbide nanowires can significantly improve the scratch resistance of the glaze layer and reduce wear during daily use.

[0137] In Comparative Example 4, the composite silicon carbide nanowires prepared without adding hydroxypropyl methylcellulose were added to the full-polished glaze. The anti-fouling performance, mechanical properties and glossiness of the glazed tiles prepared decreased, proving that the magnesium aluminum spinel powder was evenly coated on the surface of the modified silicon carbide nanowires, which could improve the dispersibility of fine-particle magnesium aluminum spinel powder in the full-polished glaze. During the firing process, the modified silicon carbide nanowires could be evenly filled into the full-polished glaze layer through the magnesium aluminum spinel powder, thereby improving the density, mechanical properties and glossiness of the glaze layer.

[0138] In comparative example 5, composite silicon carbide nanowires prepared without adding magnesium aluminum spinel powder were added to the full-polished glaze. The anti-fouling performance, mechanical properties and glossiness of the glazed tiles prepared were reduced, proving that magnesium aluminum spinel powder can provide more alumina components. The alumina components can capture the free oxygen in the full-polished glaze to form a four-coordinate system and enter the silicon-oxygen network structure of the full-polished glaze, which is helpful for the formation of the glaze network structure, improves the chemical stability, hardness and elasticity, and can avoid the large difference in the expansion coefficient of the glaze layer and the ceramic tile body. The glaze layer is subjected to a large internal stress, causing deformation during firing, thereby improving the anti-fouling performance, glossiness and mechanical properties of the glaze layer.

[0139] Throughout the specification, references to terms such as "one embodiment," "example," or "specific example" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0140] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in similar ways. As long as they do not deviate from the invention or exceed the scope defined by the claims, they should all fall within the scope of protection of the present invention.

Claims

1. A high-transparency and anti-fouling full-polished glaze, characterized in that: The invention comprises the following raw materials in parts by weight: 25-30 parts of smoky quartz feldspar, 5-10 parts of zinc oxide, 10-15 parts of barium carbonate, 2-5 parts of composite silicon carbide nanowires, 8-12 parts of calcined talc, 8-10 parts of kaolin, 8-10 parts of corundum, 23-27 parts of glass frit and 1-3 parts of zirconium silicate.

2. The high-transparency and anti-fouling full-polished glaze according to claim 1, characterized in that: The composite silicon carbide nanowires are specifically prepared by the following steps: A1. The silicon carbide nanowires were added to a nitric acid solution and a sulfuric acid solution, etched, removed, washed, and dried to obtain acid-etched silicon carbide nanowires; A2. Add zirconium oxychloride octahydrate and acid-etched silicon carbide nanowires to deionized water and stir evenly. Then add ammonia, glycine, and potassium chloride. After stirring, the reaction is hydrothermally reacted at 170-190°C for 20-22 hours, cooled to room temperature, filtered, washed, and dried to obtain modified silicon carbide nanowires. A3. Add modified silicon carbide nanowires, magnesium aluminum spinel powder, and hydroxypropyl methylcellulose to ethanol, stir evenly, heat to 80-90°C, continue stirring until the solvent evaporates, and cool to room temperature to obtain composite silicon carbide nanowires.

3. The high-transparency and anti-fouling full-polished glaze according to claim 2, characterized in that: In step A1, the mass ratio of the silicon carbide nanowires, the nitric acid solution and the sulfuric acid solution is (5-6):(25-35):(25-35).

4. The high-transparency and anti-fouling full-polished glaze according to claim 2, characterized in that: In step A2, the mass ratio of the zirconium oxychloride octahydrate, acid-etched silicon carbide nanowires, deionized water, ammonia water, glycine and potassium chloride is (0.4-0.6):(1.4-1.6):(90-110):(1.5-2.5):(0.3-0.5):(0.7-0.9).

5. The high-transparency and anti-fouling full-polished glaze according to claim 2, characterized in that: In step A3, the mass ratio of the modified silicon carbide nanowires, magnesium aluminum spinel powder, hydroxypropyl methylcellulose and ethanol is (2.4-2.6):(1-1.2):(0.2-0.4):(38-42).

6. A method for preparing a high-transparency, anti-fouling, full-polished glaze according to any one of claims 1 to 5, characterized in that: The method comprises the following preparation steps: Smoky quartz feldspar, zinc oxide, barium carbonate, composite silicon carbide nanowires, calcined talc, kaolin, corundum, glass frit and zirconium silicate are mixed evenly, crushed and passed through a 350-400 mesh sieve to obtain a high-transparency and anti-fouling full-polished glaze.

7. A method for preparing glazed tiles, characterized in that: The high-transparency and anti-fouling full-polished glaze according to any one of claims 1 to 5 is prepared, comprising the following preparation steps: S1. The high-transparency anti-fouling full-polished glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate and water were mixed and ball-milled to obtain a full-polished glaze slurry; S2. Apply the full-glaze slurry to the glazed tile base by pouring glaze, and obtain the glazed tile after drying, firing and polishing.

8. The method for preparing a glazed tile according to claim 7, characterized in that: In step S1, the mass ratio of the high-transparency and anti-fouling full-polished glaze, sodium carboxymethyl cellulose, sodium tripolyphosphate and water is (70-75):(0.1-0.2):(0.2-0.3):(30-35).

9. The method for preparing a glazed tile according to claim 7, characterized in that: In step S2, the glaze specific gravity is 1.5-1.6, and the glaze amount can be 500-550g / m 2 .

10. The method for preparing a glazed tile according to claim 7, characterized in that: In step S2, the drying temperature is 80-110°C and the drying time is 20-30 minutes; The firing temperature is 1200-1220°C and the firing time is 60-80 minutes; The polishing is performed using diamond particles with a particle size of 800-1000 mesh, a polishing time of 4-6 minutes, and a polishing pressure of 0.03-0.1 MPa.